EP3425671B1 - Nanorod production method - Google Patents

Nanorod production method Download PDF

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Publication number
EP3425671B1
EP3425671B1 EP17760252.1A EP17760252A EP3425671B1 EP 3425671 B1 EP3425671 B1 EP 3425671B1 EP 17760252 A EP17760252 A EP 17760252A EP 3425671 B1 EP3425671 B1 EP 3425671B1
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Prior art keywords
layer
nanorod
substrate
nanomaterial
manufacturing
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German (de)
French (fr)
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EP3425671A4 (en
EP3425671A1 (en
Inventor
Young Rag Do
Yeon Goog Sung
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Samsung Display Co Ltd
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Samsung Display Co Ltd
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Priority to EP22161510.7A priority Critical patent/EP4044248A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Definitions

  • the present invention relates to a method of manufacturing a nanorod and a nanorod produced thereby.
  • a nanorod is a nano-sized structure having a diameter in the range of several tens of nanometers to several hundreds of nanometers and a large aspect ratio, and a device employing the nanorod is used in various fields such as a field effect transistor (FET), a field emission device (FED), a light emitting diode (LED), a solar cell, a gas sensor, a chemical sensor, a biosensor, and the like according to applications.
  • FET field effect transistor
  • FED field emission device
  • LED light emitting diode
  • solar cell a gas sensor
  • gas sensor a chemical sensor
  • biosensor a biosensor
  • a synthesis of the nanorod may be broadly divided into two methods: a vapor method using a vapor-liquid-solid (VLS) mechanism employing a metal catalyst and a liquid method using a solution.
  • VLS vapor-liquid-solid
  • the vapor method is a method such that a state of a material is changed into a gaseous state using high heat, and atoms in the gaseous state condense to synthesize nanorods of various shapes.
  • the vapor method makes it difficult to control sizes and properties of nanorods and to uniformly arrange the synthesized nanorods.
  • a crystal structure and an optical characteristic of a nanorod which is produced by the liquid method, are poor due to a large number of defects, as compared to the nanorod synthesized by the vapor method, and similar to the vapor method, there is a problem in that arrangement and formation of electrodes are difficult.
  • a surface crack may occur in a conventional process of separating a nanorod from a substrate, and damage and thermal damage may be caused by strong heat energy and heat transfer.
  • the present invention is directed to providing a nanorod production method capable of minimizing a defective rate of a nanorod and producing a high quality nanorod, and a nanorod produced thereby.
  • the invention provides a nanorod production method including providing a growth substrate and a support substrate, epitaxial growing a nanomaterial layer on one surface of the growth substrate, forming a sacrificial layer on one surface of the support substrate, bonding the nanomaterial layer to the sacrificial layer, separating the growth substrate from the nanomaterial layer, flattening the nanomaterial layer, etching the nanomaterial layer to form a nanorod, and separating the nanorod by removing the sacrificial layer.
  • the growth substrate may include at least one among a glass substrate, a quartz substrate, a sapphire substrate, a plastic substrate, and a bendable flexible polymer film.
  • the growth substrate may include at least one among gallium nitride (GaN), silicon carbide (SiC), zinc oxide (ZnO), silicon (Si), gallium phosphide (GaP), spinel (MgAl2O4), magnesium oxide (MgO), lithium aluminate (LiAlO2), lithium gallate (LiGaO2), gallium arsenide (GaAs), aluminum nitride (AlN), indium phosphide (InP), and copper (Cu).
  • the support substrate may include at least one among the sapphire substrate, the glass substrate, a silicon carbide substrate, a silicon substrate, and a conductive substrate made of a metal material.
  • the nanomaterial layer may include at least one among ZnO, GaN, GaAs, SiC, tin oxide (SnO2), GaP, InP, zinc selenide (ZnSe), molybdenum disulfide (MoS2), and Si.
  • the nanomaterial layer may be epitaxially grown by metal organic chemical vapor deposition (MOCVD).
  • MOCVD metal organic chemical vapor deposition
  • the epitaxial growing of the nanomaterial layer on one surface of the growth substrate may include controlling a length of the nanorod by adjusting a deposition thickness of the nanomaterial layer.
  • the sacrificial layer may include an insulating layer for bonding to the nanomaterial layer and a metal layer deposited on an upper surface of the insulating layer to bond the insulating layer.
  • the metal layer of the sacrificial layer may be made of gold (Au), titanium (Ti), or iron (Fe), and the insulating layer of the sacrificial layer may be made of, silicon oxide (SiO2), or silicon nitride (SiN).
  • the separating of the growth substrate from the nanomaterial layer may include separating the growth substrate from the nanomaterial layer using one among a laser lift-off (LLO) method, a chemical lift-off (CLO) method, and an electrochemical lift-off (ELO) method.
  • LLO laser lift-off
  • CLO chemical lift-off
  • ELO electrochemical lift-off
  • the flattening of the nanomaterial layer may include flattening the nanomaterial layer separated from the growth substrate using chemical mechanical polishing (CMP).
  • CMP chemical mechanical polishing
  • the separating of the nanorod by removing the sacrificial layer may include removing the sacrificial layer using a buffered oxide etchant (BOE).
  • BOE buffered oxide etchant
  • the separating of the nanorod by removing the sacrificial layer may include removing the sacrificial layer using a metal etchant.
  • a method of manufacturing a nanorod and a nanorod produced thereby include a sacrificial layer such that a defective rate of a nanorod can be minimized by easily separating the nanorod during a process of separating the nanorod from a support substrate, thereby producing a high quality nanorod.
  • the terms “comprising,” “including,” “having,” or the like are used to specify that a feature, a number, a step, an operation, a component, an element, or a combination thereof described herein exists, and it should be understood that they do not preclude the presence or addition probability of one or more other features, numbers, steps, operations, components, elements, or combinations thereof in advance.
  • a portion of a layer, a film, a region, a plate, or the like is referred to as being "on” another portion, this includes not only a case in which the portion is “directly on” another portion but also a case in which yet another portion is present between the portion and another portion.
  • FIG. 1 is a flowchart illustrating a method of manufacturing a nanorod according to one embodiment of the present invention.
  • FIGS. 2A to 2G are cross-sectional views sequentially illustrating a process of producing a nanorod using the method of manufacturing a nanorod according to one embodiment of the present invention.
  • the method of manufacturing a nanorod includes providing a growth substrate and a support substrate (S10), epitaxial growing a nanomaterial layer on one surface of the growth substrate (S20), forming a sacrificial layer on one surface of the support substrate (S30), bonding the nanomaterial layer to the sacrificial layer (S40), separating the growth substrate from the nanomaterial layer (S50), flattening the nanomaterial layer (S60), forming a nanorod by etching the nanomaterial layer (S70), and separating the nanorod by removing the sacrificial layer (S80).
  • the method of manufacturing a nanorod according to the present invention is capable of minimizing a defective rate of a nanorod, which is caused by a process of separating a nanorod 1 from a support substrate 13, and producing a high quality nanorod.
  • a growth substrate 11 is provided to grow a nanomaterial layer 15 and the support substrate 13 is provided to support and form sacrificial layers 17 and 19.
  • the growth substrate 11 may include at least one among a glass substrate, a quartz substrate, a sapphire substrate, a plastic substrate, and a bendable flexible polymer film. Further, the growth substrate may include a transmissive substrate.
  • the growth substrate may include at least one among gallium nitride (GaN), silicon carbide (SiC), zinc oxide (ZnO), silicon (Si), gallium phosphide (GaP), spinel (MgAl 2 O 4 ), magnesium oxide (MgO), lithium aluminate (LiAlO 2 ), lithium gallate (LiGaO 2 ), gallium arsenide (GaAs), aluminum nitride (AlN), indium phosphide (InP), and copper (Cu).
  • the growth substrate 11 is not limited as long as the nanomaterial layer 15 can be epitaxially grown thereon.
  • the support substrate 13 may include one among a sapphire substrate, a glass substrate, a silicon carbide substrate, a silicon substrate, and a conductive substrate made of a metal material. Further, the support substrate 13 may include a circuit board such as a printed circuit board (PCB) or a ceramic substrate containing a ceramic.
  • PCB printed circuit board
  • the nanomaterial layer 15 which is a material of the nanorod 1 is epitaxially grown on one surface of the growth substrate 11.
  • the epitaxial growing of the nanomaterial layer on one surface of the growth substrate (S20) may include controlling a length of the nanorod by adjusting a deposition thickness of the nanomaterial layer (S21).
  • the epitaxial growing of the nanomaterial layer on one surface of the growth substrate (S20) includes epitaxial growing the nanomaterial layer 15 on an upper surface of the growth substrate 11.
  • the epitaxial growth refers to a growth of a crystal of a same material or a different material on the particular crystal substrate in a specific direction, and the epitaxial growth is referred to as epitaxy.
  • a growth of a crystal of a same material on the substrate is referred to as homoepitaxy or simply referred to as EPI, whereas a growth of a crystal of a material, which is different from a material of a substrate, on the substrate is referred to as heteroepitaxy.
  • the nanomaterial layer 15 is a nano material constituting the nanorod 1, and the nanomaterial layer 15 may be made of one among ZnO, GaN, GaAs, SiC, tin oxide (SnO 2 ), GaP, zinc selenide (ZnSe), molybdenum disulfide (MoS 2 ), and Si, but the present invention is not limited thereto.
  • the nanomaterial layer 15 may be made of any kind of nanomaterial which can be vertically grown and constitute a nanorod having a large aspect ratio.
  • vapor deposition used in the epitaxial growing of the nanomaterial layer on one surface of the growth substrate (S20) may include at least one among atomic layer deposition (ALD), reactive sputtering, ion implantation, magnetron sputtering, laser ablation, ion beam deposition, chemical vapor deposition (CVD), and plasma enhanced CVD.
  • ALD atomic layer deposition
  • CVD chemical vapor deposition
  • MOCVD metal organic CVD
  • the nanomaterial layer 15 may be epitaxially grown using an MOCVD apparatus.
  • a compound having an alkyl group such as methyl or ethyl may be used as a raw material of an organometallic compound, such as trimethylgallium (Ga(CH 3 ) 3 ), trimethylaluminum (Al(CH 3 ) 3 ), and triethyl phosphate ((C 2 H 5 O) 3 PO), used in the MOCVD apparatus.
  • an organometallic compound such as trimethylgallium (Ga(CH 3 ) 3 ), trimethylaluminum (Al(CH 3 ) 3 ), and triethyl phosphate ((C 2 H 5 O) 3 PO), used in the MOCVD apparatus.
  • the nanomaterial layer 15 is a layer for forming the nanorod 1 through a subsequent process.
  • a thickness of the nanomaterial layer 15 corresponds to a length of the nanorod 1 formed in the subsequent process so that a deposition thickness of the nanomaterial layer 15 is controlled to adjust the length of the nanorod 1.
  • a buffer layer (not shown) required for the epitaxial growth may further be formed between the growth substrate 11 and the nanomaterial layer 15 in one embodiment of the present invention. At this point, the buffer layer may be formed to minimize a lattice mismatch between the growth substrate 11 and the nanomaterial layer 15.
  • a sacrificial layer is formed on one surface of the support substrate 13, e.g., on an upper surface of the support substrate 13 as shown in FIG. 2B .
  • the sacrificial layer may include the metal layer 19 and the insulating layer 17 and the metal layer 19 may be made of a metal such as gold (Au), titanium (Ti), or iron (Fe), and the insulating layer 17 may be made of silicon oxide (SiO 2 ), or silicon nitride (SiN), but the present invention is not limited thereto.
  • the sacrificial layer may be deposited as a thin metal layer 19 on an insulating layer to bond the nanomaterial layer 15 to the insulating layer 17.
  • a bonding layer (not shown) may be provided on the upper surface of the support substrate 13 to bond the support substrate 13 to the sacrificial layer, but when the sacrificial layer is configured with a structure or a material capable of being bonded to the support substrate 13 without the bonding layer, the bonding layer may be omitted.
  • the nanomaterial layer 15 is bonded to the insulating layer by bonding an upper surface of the nanomaterial layer 15 to an upper surface of the metal layer 19.
  • the metal layer 19 and the insulating layer 17, which are the sacrificial metal layer, may be etch stop layers when the resultant nanomaterial layer is etched to form a nanorod.
  • an etchant for the nanomaterial layer 15 should be prevented from infiltrating into the support substrate 13.
  • the growth substrate 11 is separated from the nanomaterial layer 15.
  • a method of separating the growth substrate 11 from the nanomaterial layer 15 may include a laser lift-off (LLO) method, a chemical lift-off (CLO) method, and an electrochemical lift-off (ELO) method.
  • LLO laser lift-off
  • CLO chemical lift-off
  • ELO electrochemical lift-off
  • the LLO method is a method of growing the nanomaterial layer 15 on the growth substrate 11, bonding the sacrificial layer onto the nanomaterial layer, and separating the nanomaterial layer from the growth substrate 11 by irradiating a laser beam.
  • the CLO method is a method of growing another sacrificial layer on the growth substrate 11, growing the nanomaterial layer 15, bonding the sacrificial layer onto the nanomaterial layer 15, and separating the nanomaterial layer 15 from the growth substrate 11 using an etchant. At this point, the etchant selectively etches the another sacrificial layer.
  • the ELO method grows the nanomaterial layer 15 on the growth substrate 11 and forms a porous nanomaterial layer 15 through electrochemical etching using a metal anode. Then, the ELO method regrows the nanomaterial layer 15, bonds the sacrificial layer onto the nanomaterial layer, and separates the nanomaterial layer from the growth substrate.
  • flattening may be performed by a chemical mechanical polishing (CMP).
  • CMP chemical mechanical polishing
  • the nanomaterial layer 15 is selectively etched by the etchant with or without injecting the etchant to form the nanorod 1.
  • a mask material layer which is selectively etched with the nanomaterial layer 15 is formed, and the mask material layer may be formed as an insulating layer made of SiO 2 or SiN, but the present invention is not limited thereto.
  • the etchant may include sulfuric acid, phosphoric acid, potassium hydroxide, or sodium hydroxide.
  • the nanomaterial layer 15 is dry-etched in a top-down method to form the nanorod 1 which is vertically grown.
  • the top-down method is a method of implementing a display in a one-to-one correspondence manner in which a single micro light emitting diode (LED) element, which is manufactured in a top-down manner, is disposed at a position of a sub-pixel of a large-area glass substrate. However, one end portion of the nanorod 1 is bonded to the sacrificial layer.
  • LED micro light emitting diode
  • an etching gas used for the dry etching may include chlorine (Cl 2 ) or a hydrocarbon (CH 4 ) based gas, but the present invention is not limited thereto.
  • the sacrificial layer when the nanomaterial layer 15 is etched with the etchant, serves as an etch stop layer that is not etched by the etchant.
  • the etching process may be performed by dry etching or wet etching.
  • dry etching allows unidirectional etching
  • wet etching allows isotropic etching so that etching may be performed in any direction.
  • the nanorod 1 is easily separated from the support substrate 13 by removing the sacrificial layer bonded to one end portion of the nanorod 1.
  • the nanorod production method can minimize a defective rate of the nanorod and produce a high quality nanorod.
  • the sacrificial layer is made of SiO 2 , which is the insulating layer 17
  • the sacrificial layer may be removed using a buffered oxide etchant (BOE).
  • BOE buffered oxide etchant
  • hydrofluoric acid (HF) of the etchant selectively reacts with SiO 2 or SiN to form silicon tetrafluoride (SiF 4 ) such that the sacrificial layer is removed.
  • the sacrificial layer When the sacrificial layer is the metal layer 19, the sacrificial layer may be removed using a metal etchant. At this point, a method of removing the sacrificial layer through etching may remove the sacrificial layer by immersing the support substrate in the BOE.
  • a nanorod production method include a sacrificial layer such that a defective rate of a nanorod can be minimized by easily separating the nanorod during a process of separating the nanorod from a support substrate, thereby producing a high quality nanorod.
  • a nanorod production method capable of minimizing a defective rate of a nanorod and producing a high quality nanorod, and a nanorod produced thereby.

Description

    [Technical Field]
  • The present invention relates to a method of manufacturing a nanorod and a nanorod produced thereby.
    • [Background Art]
  • A nanorod is a nano-sized structure having a diameter in the range of several tens of nanometers to several hundreds of nanometers and a large aspect ratio, and a device employing the nanorod is used in various fields such as a field effect transistor (FET), a field emission device (FED), a light emitting diode (LED), a solar cell, a gas sensor, a chemical sensor, a biosensor, and the like according to applications.
  • A synthesis of the nanorod may be broadly divided into two methods: a vapor method using a vapor-liquid-solid (VLS) mechanism employing a metal catalyst and a liquid method using a solution.
  • The vapor method is a method such that a state of a material is changed into a gaseous state using high heat, and atoms in the gaseous state condense to synthesize nanorods of various shapes. The vapor method makes it difficult to control sizes and properties of nanorods and to uniformly arrange the synthesized nanorods.
  • Further, a crystal structure and an optical characteristic of a nanorod, which is produced by the liquid method, are poor due to a large number of defects, as compared to the nanorod synthesized by the vapor method, and similar to the vapor method, there is a problem in that arrangement and formation of electrodes are difficult.
  • Conventional methods of producing a nanorod include chemical polymerization, electrochemical polymerization, chemical vapor deposition (CVD), and carbothermal reduction, but the conventional methods have many restrictions which require a high synthesis temperature, a reaction time, expensive vacuum equipment, the use of a harmful gas, and the like in order to obtain a high-quality nanorod.
  • Further, a surface crack may occur in a conventional process of separating a nanorod from a substrate, and damage and thermal damage may be caused by strong heat energy and heat transfer.
    • [Disclosure] [Technical Problem]
  • The present invention is directed to providing a nanorod production method capable of minimizing a defective rate of a nanorod and producing a high quality nanorod, and a nanorod produced thereby.
    • [Technical Solution]
  • The invention provides a nanorod production method including providing a growth substrate and a support substrate, epitaxial growing a nanomaterial layer on one surface of the growth substrate, forming a sacrificial layer on one surface of the support substrate, bonding the nanomaterial layer to the sacrificial layer, separating the growth substrate from the nanomaterial layer, flattening the nanomaterial layer, etching the nanomaterial layer to form a nanorod, and separating the nanorod by removing the sacrificial layer.
  • The growth substrate may include at least one among a glass substrate, a quartz substrate, a sapphire substrate, a plastic substrate, and a bendable flexible polymer film.
  • The growth substrate may include at least one among gallium nitride (GaN), silicon carbide (SiC), zinc oxide (ZnO), silicon (Si), gallium phosphide (GaP), spinel (MgAl2O4), magnesium oxide (MgO), lithium aluminate (LiAlO2), lithium gallate (LiGaO2), gallium arsenide (GaAs), aluminum nitride (AlN), indium phosphide (InP), and copper (Cu).
  • The support substrate may include at least one among the sapphire substrate, the glass substrate, a silicon carbide substrate, a silicon substrate, and a conductive substrate made of a metal material.
  • The nanomaterial layer may include at least one among ZnO, GaN, GaAs, SiC, tin oxide (SnO2), GaP, InP, zinc selenide (ZnSe), molybdenum disulfide (MoS2), and Si.
  • The nanomaterial layer may be epitaxially grown by metal organic chemical vapor deposition (MOCVD).
  • The epitaxial growing of the nanomaterial layer on one surface of the growth substrate may include controlling a length of the nanorod by adjusting a deposition thickness of the nanomaterial layer.
  • The sacrificial layer may include an insulating layer for bonding to the nanomaterial layer and a metal layer deposited on an upper surface of the insulating layer to bond the insulating layer.
  • The metal layer of the sacrificial layer may be made of gold (Au), titanium (Ti), or iron (Fe), and the insulating layer of the sacrificial layer may be made of, silicon oxide (SiO2), or silicon nitride (SiN).
  • The separating of the growth substrate from the nanomaterial layer may include separating the growth substrate from the nanomaterial layer using one among a laser lift-off (LLO) method, a chemical lift-off (CLO) method, and an electrochemical lift-off (ELO) method.
  • The flattening of the nanomaterial layer may include flattening the nanomaterial layer separated from the growth substrate using chemical mechanical polishing (CMP).
  • When the insulating layer of the sacrificial layer is made of SiO2, the separating of the nanorod by removing the sacrificial layer may include removing the sacrificial layer using a buffered oxide etchant (BOE).
  • When the sacrificial layer is made of a metal layer, the separating of the nanorod by removing the sacrificial layer may include removing the sacrificial layer using a metal etchant.
    • [Advantageous Effects]
  • A method of manufacturing a nanorod and a nanorod produced thereby, according to an exemplary embodiment of the present invention, include a sacrificial layer such that a defective rate of a nanorod can be minimized by easily separating the nanorod during a process of separating the nanorod from a support substrate, thereby producing a high quality nanorod.
  • US 2013/048945 A1 , EP 2 704 215 A2 and US 2010/048025 A1 describe methods for manufacturing nanorods.
    • [Description of Drawings]
    • FIG. 1 is a flowchart illustrating a nanorod production method according to one embodiment of the present invention.
    • FIGS. 2A to 2G are cross-sectional views sequentially illustrating a process of producing a nanorod using the nanorod production method according to one embodiment of the present invention.
    [Modes of the Invention]
  • Hereinafter, embodiments of the present invention will be fully described in detail which is suitable for easy implementation by those skilled in the art to which the present invention pertains with reference to the accompanying drawings. The present invention may be implemented in various different forms, and thus it is not limited to embodiments which will be described herein. In the drawings, some portions not related to the description will be omitted and not be shown in order to clearly describe the present invention, and the same reference numerals are given to the same or similar components throughout this disclosure.
  • In this description, the terms "comprising," "including," "having," or the like are used to specify that a feature, a number, a step, an operation, a component, an element, or a combination thereof described herein exists, and it should be understood that they do not preclude the presence or addition probability of one or more other features, numbers, steps, operations, components, elements, or combinations thereof in advance. Further, when a portion of a layer, a film, a region, a plate, or the like is referred to as being "on" another portion, this includes not only a case in which the portion is "directly on" another portion but also a case in which yet another portion is present between the portion and another portion. Contrarily, when a portion of a layer, a film, a region, a plate, or the like is referred to as being "under" another portion, this includes not only a case in which the portion is "directly under" another portion but also a case in which yet another portion is present between the portion and another portion.
  • Hereinafter, a nanorod production method and a nanorod produced thereby according to one embodiment of the present invention will be described in detail with reference to the drawings.
  • FIG. 1 is a flowchart illustrating a method of manufacturing a nanorod according to one embodiment of the present invention. FIGS. 2A to 2G are cross-sectional views sequentially illustrating a process of producing a nanorod using the method of manufacturing a nanorod according to one embodiment of the present invention.
  • Referring to FIG. 1, the method of manufacturing a nanorod includes providing a growth substrate and a support substrate (S10), epitaxial growing a nanomaterial layer on one surface of the growth substrate (S20), forming a sacrificial layer on one surface of the support substrate (S30), bonding the nanomaterial layer to the sacrificial layer (S40), separating the growth substrate from the nanomaterial layer (S50), flattening the nanomaterial layer (S60), forming a nanorod by etching the nanomaterial layer (S70), and separating the nanorod by removing the sacrificial layer (S80).
  • Accordingly, the method of manufacturing a nanorod according to the present invention is capable of minimizing a defective rate of a nanorod, which is caused by a process of separating a nanorod 1 from a support substrate 13, and producing a high quality nanorod.
  • Referring to FIGS. 1 and 2A, in the providing of the growth substrate and the support substrate (S10), a growth substrate 11 is provided to grow a nanomaterial layer 15 and the support substrate 13 is provided to support and form sacrificial layers 17 and 19.
  • Meanwhile, referring to FIG. 2A, the growth substrate 11 may include at least one among a glass substrate, a quartz substrate, a sapphire substrate, a plastic substrate, and a bendable flexible polymer film. Further, the growth substrate may include a transmissive substrate.
  • In this case, the growth substrate may include at least one among gallium nitride (GaN), silicon carbide (SiC), zinc oxide (ZnO), silicon (Si), gallium phosphide (GaP), spinel (MgAl2O4), magnesium oxide (MgO), lithium aluminate (LiAlO2), lithium gallate (LiGaO2), gallium arsenide (GaAs), aluminum nitride (AlN), indium phosphide (InP), and copper (Cu). However, the growth substrate 11 is not limited as long as the nanomaterial layer 15 can be epitaxially grown thereon.
  • Meanwhile, referring to FIG. 2A, the support substrate 13 may include one among a sapphire substrate, a glass substrate, a silicon carbide substrate, a silicon substrate, and a conductive substrate made of a metal material. Further, the support substrate 13 may include a circuit board such as a printed circuit board (PCB) or a ceramic substrate containing a ceramic.
  • Referring to FIGS. 1 and 2B, in the epitaxial growing of the nanomaterial layer on one surface of the growth substrate (S20), the nanomaterial layer 15 which is a material of the nanorod 1 is epitaxially grown on one surface of the growth substrate 11.
  • In this case, the epitaxial growing of the nanomaterial layer on one surface of the growth substrate (S20) may include controlling a length of the nanorod by adjusting a deposition thickness of the nanomaterial layer (S21).
  • Further, as shown in FIG. 2B, the epitaxial growing of the nanomaterial layer on one surface of the growth substrate (S20) includes epitaxial growing the nanomaterial layer 15 on an upper surface of the growth substrate 11.
  • At this point, the epitaxial growth refers to a growth of a crystal of a same material or a different material on the particular crystal substrate in a specific direction, and the epitaxial growth is referred to as epitaxy.
  • Further, a growth of a crystal of a same material on the substrate is referred to as homoepitaxy or simply referred to as EPI, whereas a growth of a crystal of a material, which is different from a material of a substrate, on the substrate is referred to as heteroepitaxy.
  • Meanwhile, the nanomaterial layer 15 is a nano material constituting the nanorod 1, and the nanomaterial layer 15 may be made of one among ZnO, GaN, GaAs, SiC, tin oxide (SnO2), GaP, zinc selenide (ZnSe), molybdenum disulfide (MoS2), and Si, but the present invention is not limited thereto.
  • In one embodiment of the present invention, the nanomaterial layer 15 may be made of any kind of nanomaterial which can be vertically grown and constitute a nanorod having a large aspect ratio.
  • Meanwhile, referring to FIG. 1, vapor deposition used in the epitaxial growing of the nanomaterial layer on one surface of the growth substrate (S20) may include at least one among atomic layer deposition (ALD), reactive sputtering, ion implantation, magnetron sputtering, laser ablation, ion beam deposition, chemical vapor deposition (CVD), and plasma enhanced CVD.
  • However, metal organic CVD (MOCVD) may be preferably used for the epitaxial growth according to one embodiment of the present invention. That is, the nanomaterial layer 15 may be epitaxially grown using an MOCVD apparatus.
  • In this case, a compound having an alkyl group such as methyl or ethyl may be used as a raw material of an organometallic compound, such as trimethylgallium (Ga(CH3)3), trimethylaluminum (Al(CH3)3), and triethyl phosphate ((C2H5O)3PO), used in the MOCVD apparatus.
  • Meanwhile, the nanomaterial layer 15 is a layer for forming the nanorod 1 through a subsequent process. In one embodiment of the present invention, in the controlling of the length of the nanorod by adjusting the deposition thickness of the nanomaterial layer (S21), a thickness of the nanomaterial layer 15 corresponds to a length of the nanorod 1 formed in the subsequent process so that a deposition thickness of the nanomaterial layer 15 is controlled to adjust the length of the nanorod 1.
  • Although not shown in the drawing, a buffer layer (not shown) required for the epitaxial growth may further be formed between the growth substrate 11 and the nanomaterial layer 15 in one embodiment of the present invention. At this point, the buffer layer may be formed to minimize a lattice mismatch between the growth substrate 11 and the nanomaterial layer 15.
  • Referring to FIGS. 1 and 2B, in the forming of the sacrificial layer on one surface of the support substrate (S30), a sacrificial layer is formed on one surface of the support substrate 13, e.g., on an upper surface of the support substrate 13 as shown in FIG. 2B.
  • At this point, in one embodiment of the present invention, the sacrificial layer may include the metal layer 19 and the insulating layer 17 and the metal layer 19 may be made of a metal such as gold (Au), titanium (Ti), or iron (Fe), and the insulating layer 17 may be made of silicon oxide (SiO2), or silicon nitride (SiN), but the present invention is not limited thereto.
  • Further, the sacrificial layer may be deposited as a thin metal layer 19 on an insulating layer to bond the nanomaterial layer 15 to the insulating layer 17.
  • Alternatively, when the sacrificial layer is formed on the upper surface of the support substrate 13, a bonding layer (not shown) may be provided on the upper surface of the support substrate 13 to bond the support substrate 13 to the sacrificial layer, but when the sacrificial layer is configured with a structure or a material capable of being bonded to the support substrate 13 without the bonding layer, the bonding layer may be omitted.
  • Referring to FIGS. 1 and 2C, in the bonding of the nanomaterial layer to the sacrificial layer (S40), the nanomaterial layer 15 is bonded to the insulating layer by bonding an upper surface of the nanomaterial layer 15 to an upper surface of the metal layer 19.
  • The metal layer 19 and the insulating layer 17, which are the sacrificial metal layer, may be etch stop layers when the resultant nanomaterial layer is etched to form a nanorod.
  • Therefore, an etchant for the nanomaterial layer 15 should be prevented from infiltrating into the support substrate 13.
  • Meanwhile, referring to FIGS. 1 and 2D, in the separating of the growth substrate from the nanomaterial layer (S50), the growth substrate 11 is separated from the nanomaterial layer 15.
  • At this point, a method of separating the growth substrate 11 from the nanomaterial layer 15 may include a laser lift-off (LLO) method, a chemical lift-off (CLO) method, and an electrochemical lift-off (ELO) method.
  • The LLO method is a method of growing the nanomaterial layer 15 on the growth substrate 11, bonding the sacrificial layer onto the nanomaterial layer, and separating the nanomaterial layer from the growth substrate 11 by irradiating a laser beam.
  • The CLO method is a method of growing another sacrificial layer on the growth substrate 11, growing the nanomaterial layer 15, bonding the sacrificial layer onto the nanomaterial layer 15, and separating the nanomaterial layer 15 from the growth substrate 11 using an etchant. At this point, the etchant selectively etches the another sacrificial layer.
  • The ELO method grows the nanomaterial layer 15 on the growth substrate 11 and forms a porous nanomaterial layer 15 through electrochemical etching using a metal anode. Then, the ELO method regrows the nanomaterial layer 15, bonds the sacrificial layer onto the nanomaterial layer, and separates the nanomaterial layer from the growth substrate.
  • In the flattening of the nanomaterial layer (S60), flattening may be performed by a chemical mechanical polishing (CMP).
  • Meanwhile, referring to FIGS. 1 and 2E, in the forming of the nanorod by etching the nanomaterial layer (S70), the nanomaterial layer 15 is selectively etched by the etchant with or without injecting the etchant to form the nanorod 1.
  • In this case, a mask material layer which is selectively etched with the nanomaterial layer 15 is formed, and the mask material layer may be formed as an insulating layer made of SiO2 or SiN, but the present invention is not limited thereto.
  • At this point, the etchant may include sulfuric acid, phosphoric acid, potassium hydroxide, or sodium hydroxide. Meanwhile, the nanomaterial layer 15 is dry-etched in a top-down method to form the nanorod 1 which is vertically grown.
  • The top-down method is a method of implementing a display in a one-to-one correspondence manner in which a single micro light emitting diode (LED) element, which is manufactured in a top-down manner, is disposed at a position of a sub-pixel of a large-area glass substrate. However, one end portion of the nanorod 1 is bonded to the sacrificial layer.
  • Here, an etching gas used for the dry etching may include chlorine (Cl2) or a hydrocarbon (CH4) based gas, but the present invention is not limited thereto. In one embodiment of the present invention, when the nanomaterial layer 15 is etched with the etchant, the sacrificial layer serves as an etch stop layer that is not etched by the etchant.
  • Alternatively, the etching process may be performed by dry etching or wet etching. In this case, unlike wet etching, dry etching allows unidirectional etching, while wet etching allows isotropic etching so that etching may be performed in any direction.
  • Referring to FIGS. 1 and 2F, in the separating of the nanorod by removing the sacrificial layer (S80), the nanorod 1 is easily separated from the support substrate 13 by removing the sacrificial layer bonded to one end portion of the nanorod 1.
  • Consequently, the nanorod production method according to one embodiment of the present invention can minimize a defective rate of the nanorod and produce a high quality nanorod.
  • In this case, when the sacrificial layer is made of SiO2, which is the insulating layer 17, the sacrificial layer may be removed using a buffered oxide etchant (BOE).
  • At this point, hydrofluoric acid (HF) of the etchant selectively reacts with SiO2 or SiN to form silicon tetrafluoride (SiF4) such that the sacrificial layer is removed.
  • When the sacrificial layer is the metal layer 19, the sacrificial layer may be removed using a metal etchant. At this point, a method of removing the sacrificial layer through etching may remove the sacrificial layer by immersing the support substrate in the BOE.
  • A nanorod production method according to the present invention include a sacrificial layer such that a defective rate of a nanorod can be minimized by easily separating the nanorod during a process of separating the nanorod from a support substrate, thereby producing a high quality nanorod.
    • [Industrial Applicability]
  • In accordance with of the present invention, there are provided a nanorod production method capable of minimizing a defective rate of a nanorod and producing a high quality nanorod, and a nanorod produced thereby.

Claims (13)

  1. A method of manufacturing a nanorod (1), the method comprising:
    providing a growth substrate (11) and a support substrate (13);
    epitaxial growing a nanomaterial layer (15) on one surface of the growth substrate (11);
    forming a sacrificial layer on one surface of the support substrate (13);
    bonding the nanomaterial layer (15) to the sacrificial layer;
    separating the growth substrate (11) from the nanomaterial layer (15);
    flattening the nanomaterial layer (15);
    etching the nanomaterial layer (15) to form a nanorod (1); and
    separating the nanorod (1) by removing the sacrificial layer.
  2. The method of manufacturing a nanorod (1) of claim 1, wherein the growth substrate (11) includes at least one among a glass substrate, a quartz substrate, a sapphire substrate, a plastic substrate, and a bendable flexible polymer film.
  3. The method of manufacturing a nanorod (1) of claim 1, wherein the growth substrate (11) includes at least one among gallium nitride (GaN), silicon carbide (SiC), zinc oxide (ZnO), silicon (Si), gallium phosphide (GaP), spinel (MgAl2O4), magnesium oxide (MgO), lithium aluminate (LiAlO2), lithium gallate (LiGaO2), gallium arsenide (GaAs), aluminum nitride (AlN), indium phosphide (InP), and copper (Cu).
  4. The method of manufacturing a nanorod (1) of claim 1, wherein the support substrate (13) includes at least one among a sapphire substrate, a glass substrate, a silicon carbide substrate, a silicon substrate, and a conductive substrate made of a metal material.
  5. The method of manufacturing a nanorod (1) of claim 1, wherein the nanomaterial layer (15) includes at least one among zinc oxide (ZnO), gallium nitride (GaN), gallium arsenide (GaAs), silicon carbide (SiC), tin oxide (SnO2), gallium phosphide (GaP), indium phosphide (InP), zinc selenide (ZnSe), molybdenum disulfide (MoS2), and silicon (Si).
  6. The method of manufacturing a nanorod (1) of claim 1, wherein the nanomaterial layer (15) is epitaxially grown by metal organic chemical vapor deposition (MOCVD).
  7. The method of manufacturing a nanorod (1) of claim 6, wherein the epitaxial growing of the nanomaterial layer (15) on one surface of the growth substrate (11) includes controlling a length of the nanorod (1) by adjusting a deposition thickness of the nanomaterial layer (15).
  8. The method of manufacturing a nanorod (1) of claim 1, wherein the sacrificial layer includes an insulating layer (17) for bonding to the nanomaterial layer (15) and a metal layer (19) deposited on an upper surface of the insulating layer (17) to bond the insulating layer (17).
  9. The method of manufacturing a nanorod (1) of claim 8, wherein the metal layer (19) of the sacrificial layer is made of gold (Au), titanium or iron (Fe), and the insulating layer (17) of the sacrificial layer is made of silicon oxide (SiO2), or silicon nitride (SiN).
  10. The method of manufacturing a nanorod (1) of claim 1, wherein the separating of the growth substrate (11) from the nanomaterial layer (15) includes separating the growth substrate (11) from the nanomaterial layer (15) using one among a laser lift-off (LLO) method, a chemical lift-off (CLO) method, and an electrochemical lift-off (ELO) method.
  11. The method of manufacturing a nanorod (1) of claim 10, wherein the flattening of the nanomaterial layer (15) includes flattening the nanomaterial layer (15) separated from the growth substrate (11) using chemical mechanical polishing (CMP).
  12. The method of manufacturing a nanorod (1) of claim 9, wherein, when the insulating layer (17) of the sacrificial layer is made of SiO2, the separating of the nanorod (1) by removing the sacrificial layer includes removing the sacrificial layer using a buffered oxide etchant (BOE).
  13. The method of manufacturing a nanorod (1) of claim 9, wherein, the separating of the nanorod (1) by removing the sacrificial layer includes removing the metal layer (19) of the sacrificial layer using a metal etchant.
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EP3425671A4 (en) 2019-07-24
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US20190051724A1 (en) 2019-02-14
US20230056417A1 (en) 2023-02-23
CN108701710B (en) 2021-10-26
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US10580859B2 (en) 2020-03-03
US20200212178A1 (en) 2020-07-02
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EP3425671A1 (en) 2019-01-09

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